WO2005121059A1

WO2005121059A1 - Method for producing ethers

Info

Publication number: WO2005121059A1
Application number: PCT/JP2005/010504
Authority: WO
Inventors: Jin Tokuyasu; Taketoshi Okuno; Takashi Hori; Hideharu Iwasaki
Original assignee: Kuraray Co., Ltd.
Priority date: 2004-06-11
Filing date: 2005-06-08
Publication date: 2005-12-22
Also published as: CA2569017A1; EP1760061A1; JPWO2005121059A1; US7728180B2; CN1972888A; CA2569017C; US20080262272A1; EP1760061A4

Abstract

Disclosed is a method for producing ethers which is characterized in that a telomerization reaction of a conjugated diene compound in the presence of a hydroxyl compound represented by the following general formula (I): R1OH, is firstly performed in the presence of a palladium compound, a tertiary isocyanide compound represented by the following general formula (II): R2NC and a basic substance, and then continuously performed after being added with a tertiary phosphine compound represented by the following general formula (III): PR3R4R5. (In the formulae, the symbols are as defined in the description.)

Description

Specification

Method for producing ethers

Technical field

The present invention relates to a method for producing ethers by a telomerization reaction of a conjugated diene compound. The ethers produced by the present invention are useful as raw materials for various polymers and intermediates such as fragrances.

Background art

[0002] The telomerization reaction of a conjugated gen compound is a reaction in which the conjugated gen compound is oligomerized by incorporating a nucleophilic reactant such as an alcohol. For example, a reaction in which two molecules of 1,3 butadiene reacts with one molecule of a compound containing active hydrogen such as acetic acid to produce 1-acetoxy 2,7 octadiene is exemplified. In the telomery-dani reaction, it is known that a palladium compound, particularly a palladium compound coordinated with a phosphine compound, exhibits excellent activity as a catalyst for S-telomerization reaction (see Non-Patent Documents 1 and 2). ).

On the other hand, a telomerization reaction using a catalyst comprising a tertiary phosphine compound or an isocyanide compound and a nickel compound has been reported (see Patent Document 1). Further, a telomerization reaction using a palladium carbene complex in the presence of a basic substance has been reported (see Patent Document 2). Furthermore, a telomerization reaction using a catalyst comprising a primary isocyanide compound and tetrakis (triphenylphosphine) palladium (see Patent Document 3) and a telomerization reaction using a catalyst comprising a tertiary isocyanide compound and a palladium compound (see Patent Reference 4) has been reported.

[0003] Non-Patent Document 1: Niro Tsuji, "Palladium Reagents and Catalysts", published by John Wiley & Sons, p. 423-441 (1995)

Non-Patent Document 2: Angevante Chemie International Edition (Angew. Chem. Int. Ed.), Vol. 41, p. 1290-1309 (2002)

Patent Document 1: US Patent No. 3670029 Patent Document 2: Japanese Patent Publication No. 2004-534059

Patent Document 3: Japanese Patent Publication No. 48-43327 (Example 9)

Patent Document 4: JP 2005-95850 A

Disclosure of the invention

Problems to be solved by the invention

[0004] The methods described in Non-Patent Document 1 and Non-Patent Document 2 disclose a method of evaporating and separating a product and a catalyst after completion of a reaction in which a palladium catalyst coordinated with a phosphine compound has poor thermal stability. Since the catalyst decomposes to precipitate palladium black, there is a problem that it is difficult to reuse the palladium catalyst and the production cost increases.

[0005] The method described in Patent Document 1 requires high selectivity for by-products (about 10 to 30%) and low catalytic activity, and thus requires a large amount of catalyst. It is not an efficient method for producing ethers.

[0006] In the method described in Patent Document 2, it is necessary to add a large excess of a basic substance to a catalyst in which a nitrogen-containing heterocyclic carbene is coordinated with a palladium compound in order to increase the reaction efficiency. is there. However, the addition of a large excess of a basic substance causes corrosion of the reactor and blockage of the piping, and furthermore makes it difficult to maintain the stability of the catalyst.

[0007] The method described in Patent Document 3 uses a palladium compound to which a phosphine conjugate has already been coordinated. In this case, the coordination of the isocyanide compound to the palladium atom is suppressed, and the reaction is remarkably slowed down.The selectivity of the target product is lowered, and the yield is as low as about 17%. Not a way. Further, the present inventors have, in the method described in Patent Document 4, can be obtained inexpensively by industrially, low purity (1, 3-butadiene content of about 40 weight ^_0/0) of "such as crude butadiene (isobutylene Butenes, methinorea acetylene, acetylenes such as 1-butyne, and 1,3-butadiene containing impurities such as 1,2-butadiene) were used as raw materials, and it was confirmed that the reaction rate was reduced. did. That is, there is still room for improvement as a method for industrially producing ethers at low cost and with high productivity.

[0008] Thus, an object of the present invention is to provide an industrially advantageous method for producing ethers, which can provide a high conversion and a high selectivity even from a low-purity and inexpensive conjugated gen compound. There is to be.

Means for solving the problem

According to the present invention, the above object has the following general formula (I)

[Formula 1] R'OH (I)

(In the formula, R ¹ represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted realyl group.)

In the telomerization reaction of a conjugated gen compound in the presence of a hydroxy compound (hereinafter referred to as hydroxyl aldehyde compound (I)), a palladium compound represented by the general formula (II)

[Formula 2] R ² NC (II)

(In the formula, R ² represents a tertiary alkyl group which may have a substituent.)

The above reaction is carried out in the presence of a tertiary isocyanidide conjugate [hereinafter referred to as an isocyanide conjugate (II)] and a basic substance, and then represented by the general formula (III)

[Chemical Formula 3] PR ³ R ⁴ R ° (III)

(Wherein, R ³ , R ⁴ and R ⁵ each independently represent an alkyl group having from! To 10 carbon atoms.) [Hereinafter, this is referred to as a phosphine compound (III) )], Followed by a subsequent reaction, to provide a process for producing ethers.

BEST MODE FOR CARRYING OUT THE INVENTION

According to the present invention, first, a telomerization reaction of a conjugated diene compound is started in the presence of a hydroxy compound (1), a palladium compound, an isocyanide compound (II) and a basic substance, and then a phosphine compound (III) Is carried out.

[0011] Specific examples of the conjugated diene compound used in the present invention include, for example, 1,3-butadiene, isoprene, piperylene, 2,3-dimethinole-1,3-butadiene, 1,3,7-butadiene, Examples thereof include 1,3-cyclohexadiene and 1,3-cyclooctadiene. Further, the conjugated diene compound may have a low purity. For example, in the case of 1,3-butadiene, as described above, crude butadiene (butenes such as isobutylene, butenes such as isobutylene, methyl acetylene, 1-butyne, etc.) Contains impurities such as acetylenes and 1,2-butadiene 1,3-butadiene) can be used. It is well known to those skilled in the art that such crude butadiene is obtained as a C4 cut by the thermal decomposition of naphtha. The crude butadiene thus obtained can be obtained inexpensively because the step of isolating 1,3-butadiene is omitted, and when a powerful crude butadiene is used as a raw material, it is industrially very advantageous from the viewpoint of production cost. It is. The present invention is a method for producing ethers that can maintain high conversion and selectivity even when a low-purity conjugated conjugate such as crude butadiene is used as a raw material.

In the above general formula (I), the alkyl group represented by R ¹ is preferably an alkyl group having 1 to 8 carbon atoms, such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, and an isobutyl group. Examples include a tinole group, an s-butyl group, a t-butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. These substituents may have a substituent. Examples of the substituent include a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom; an aryl group such as a phenyl group, a tolyl group and a xylyl group. An alkoxyl group such as a methoxy group, an ethoxy group and an isopropoxy group; a 2-methoxyethyloxy group, a 2-ethoxyxyloxy group; a hydroxyl group. The aryl group represented by R ¹ is preferably an aryl group having 6 to 14 carbon atoms, for example, a phenyl group, a naphthyl group, a phenanthryl group, an anthracenyl group and the like. These groups may have a substituent and may be, for example, a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom; a methyl group, an ethyl group, a propyl group and an isopropyl group. Groups, butyl, isobutyl, s-butyl, t-butyl, pentyl, hexyl, heptyl, octyl and other alkyl groups; methoxy, ethoxy, isopropoxy and other alkoxyl groups; hydroxyl groups, etc. Are mentioned.

[0013] Specific examples of the hydroxyl compound (I) include, for example, methanol, ethanol, 1-propanol, 2-propanol, 2-methinol_1-propanol, 1-butanol, 2-butanol, pentano-fold. , Isopentinoleanolone, cyclopentanol, hexanol, 2_hexanol, cyclohexanol, heptanol, octanol, 2-octanol, 3-octanol, benzyl alcohol, phenethyl alcohol, phenol, ethyl Examples include ren glycol, diethylene glycol, propylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, and propylene glycol monoethyl ether.

The amount of the hydroxyl compound (I) to be used is preferably in the range of 0.1 to 10 times mol, more preferably in the range of 0.5 to 5 times mol, based on the conjugated diene compound.

Examples of the ethers obtained in the present invention include 1-methoxy-1,2,7-octadiene, 1-ethoxy-1,2,7-octadiene, 1_propoxy_2,7-octadiene, 1_butoxy-2,7-octadiene, 1_Isopentyloxy-1,2,7-octadiene, 1-cyclohexylnoroxy_2,7-octadiene, 1_phenoxy_2,7-octadiene, 1_benzinoleoxy_2,7-octadiene, 1-methoxy-1,2,7 —Dimethyl_2,7-octadiene, 1—Ethoxy-1,2,7-dimethinolee 2,7-octadiene, 1_Propoxy_2,7—dimethinole 2,7-octadiene, 1-butoxy 2,7-dimethyl-2,7-octadiene, 1-iso Pentoxy 2,7 dimethyl-2,7-octadiene, 1-cyclohexyloxy-2,7 dimethinole 2,7-octadiene, 1 phenoxy 2,7 dimethyl-2,7-octa Gen, 1 Benzyloxy 2,7 Dimethinolate 2,7-Octadien, 1-Methoxy 2,6 Dimethyl 2,7-Octadien, 1 Ethoxy 2,6 Dimethinole 2,7-Octadien, 1 Propoxy 2,6 Dimethyl 2,7 —Octactogen, 1-butoxy —2,6 Dimethinole 1,7—Octagene, 1—Isopentyxoxy 1,2,6 Dimethyl-1,2,7 Octactene, 1-Cyclohexyloxy 2,6 Dimethinole 2,7—Octogen, 1— Phenoxy 2,6 dimethyl-1,2,7-octadiene, 1-benzyloxy-1,2,6-dimethinolae 2,7-octadiene, 1-methoxy-1,3,7-dimethyl_2,7-octadiene, 1_ethoxy_3,7 —Dimethyl_2,7-octadiene, 1_propoxy-1,3,7-dimethinolee 2,7-octadiene, 1_butoxy-1,3,7_dimethinole-1,2,7-octadiene, 1_isopen Roxy _3,7-dimethinolee 2,7-octadiene, 1-cyclohexyloxy_3,7-dimethyl_2,7-octadiene, 1-phenoxy-1,3,7-dimethyl_2,7-octadiene, 1_benzyloxy-1,3 7-Dimethyl-1,2,7-octadiene, 1-Methoxy-1,3,6_dimethinole-1,2,7-Octagene, 1_Ethoxy-1,3,6-dimethinole 2,7-octadiene, 1 propoxy 3,6 dimethyl-2,7-octadiene, 1-butoxy 3,6 dimethinolee 2,7-octadiene, 1 isopentyloxy 3,6 dimethinole 2,7-octadiene, 1-cyclohexyloxy 3, 6 Dimethinolee 2,7-Otatagene, 1-Phenoxy_3, 6-Dimethyl_2,7-Octadien, 1_Benzyloxy-1,3,6-Dimethyl_2,7-Octadien, 3-Methoxy-1-2,7-Octadien, 3_ Ethoxy 1,2,7-octadiene, 3_propoxy_2,7-octadiene, 3_butoxy-1,2,7-octadiene, 3_isopenticone xy-1,2,7-octadiene, 3-cyclohexyloxy_2,7-octadiene , 3_phenoxy_2,7-octadiene, 3_benzyloxy-1,2,7-octadiene, 3-methoxy-1,2,7-dimethyl_2,7-octadiene, 3_ethoxy 2,7-Dimethinolee 2,7-Octadogen, 3_Propoxy_2,7-Dimethinole-2,7-Octadene, 3_Butoxy_2,7-Dimethyl-1,2,7-Octadene, 3-Disopentyloxy_2,7-Dimethinolee 2,7-octadiene, 3-cyclohexoxyloxy 2,7 dimethinole 2,7-octadiene, 3 phenoxy 2,7 dimethyl 2,7-otatagene, 3 benzyloxy 2,7 dimethyl 2,7 octadiene, 3 methoxy- 2,6 dimethinolee 2,7-octadiene, 3 ethoxy 2,6 dimethinolee 2,7 octadiene, 3 propoxy 2,6 dimethinolee 2,7-octadiene, 3 butoxy 2,6 dimethinolee 2,7-octadiene, 3 isopench mouth 1,6-dimethyl-2,7-octadiene, 3 cyclohexyloxy 2,6 dimethinolate 2,7-octadiene, 3 phenoxy 2,6 dimethino -2,7 octadiene, 3 benzyloxy-1,2,6-dimethinolane 2,7 octadiene, 3-methoxy-3,7 dimethyl-2,7-octadiene, 3 ethoxy 3,7 dimethyl-2,7-octadiene, 3 propoxy 3,7 dime 2,7-octanol, 3,7-butoxy 3,7-dimethinole 2,7-octadiene, 3-isopentyloxy_3,7-dimethyl_2,7-octadiene, 3-cyclohexyloxy-1,3,7 —Dimethyl_2,7-octadiene, 3-phenoxy_3,7-dimethyl-1,2,7-octadiene, 3 _benzyloxy_3,7-dimethinole 2,7-octadiene, 3-methoxy-1 3,6-dimethinole 2, 7-octadiene, 3_ethoxy_3, 6-dimethyl_2, 7-octadiene, 3_propoxy_3,6-dimethyl-1,2,7-octadiene, 3-butoxy-1,3,6-dimethyl_2,7— Octactogen, 3_isopentyloxy_3,6-dimethyl -2,7-octadiene, 3 cyclohexyloxy 3,6 dimethinole 2,7-octadiene, 3 phenoxy 3,6 dimethyl 2,7-octadiene, 3 benzyloxy-3,6 dimethyl-1,2,7-octadiene Can be

The palladium compound used in the present invention is not particularly limited as long as it does not contain a compound having a phosphorus atom. For example, palladium formate, palladium acetate, palladium chloride, palladium bromide, palladium carbonate, palladium sulfate, Palladium nitrate, sodium palladium chloride, potassium chloropalladate, palladium acetyl acetonate, bis (benzonitrile) palladium dichloride, bis (t-butyl isocyanide) palladium dichloride, bis (dibenzylideneacetone) palladium, Tris (dibenzylideneacetone) dipalladium, bis (1,5-cyclooctadiene) palladium and the like can be mentioned. Among these, it is preferable to use palladium acetate and palladium acetyl acetate in consideration of availability and economy. The amount of the palladium compound used is preferably in the range of 0.1 ppm to 100 ppm, more preferably 1 ppm to 50 ppm, per mole of the conjugated diene compound, in terms of palladium atom.

In the general formula (II), examples of the tertiary alkyl group which may have a substituent represented by R ² include a t-butyl group, a 1,1-dimethylhexyl group, a trityl group, and a 1-methylcycloalkyl group. Hexinole group and the like.

[0017] Specific examples of the isocyanide compound (II) used in the present invention include t-butyl isocyanide, t-octyl isocyanide, trityl isocyanide, 1-methylcyclohexyl isocyanide and the like. Of these, t-butyl isocyanide and t-octyl isocyanide are preferred in view of availability and economy. In the present invention, a tertiary isocyanide compound is used, and a primary isocyanide compound or a secondary isocyanide compound is not used. This is because, if a hydrogen atom is present on the carbon at the position higher than the isocyanide compound, a strong hydrogen atom is extracted by the basic substance used in the present invention, and the isocyanide compound is decomposed, so that the reaction does not proceed.

The use amount of the isocyanide compound (II) is preferably in the range of 1 to 50 mol per 1 mol of palladium atoms in the palladium compound: more preferably in the range of! To 20 mol. The basic substance used in the present invention has the general formula (IV)

[Formula 4] M (OR ⁶ ) (IV)

(In the formula, M represents an alkali metal or an alkaline earth metal, and R ⁶ represents a hydrogen atom, a group having a substituent, a group having an alkyl group or a substituent, or a group having a substituent. , Represents an aryl group, and n represents 1 when M represents an alkali metal, and represents 2 when M represents an alkaline earth metal.)

A compound represented by the general formula (V)

[0019] [Formula 5]

OR, (V)

(Wherein, R ⁷ , R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ are each independently a hydrogen atom, may have a substituent, or have an alkyl group or a substituent. A compound represented by the general formula (VI)

[0021] [Formula 6]

(Wherein, R ¹² , R ¹³ , R ^M , R ¹⁵ and R ¹⁶ each independently have a hydrogen atom, a substituent, an alkyl group or a substituent. And a aryl group.)).

In the general formulas (IV), (V) and (VI), R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ", R ¹² , R ¹³ , R", R ¹⁵ and R Examples of the alkyl group represented by ¹⁶ include a methyl group, an ethyl group, a propyl group, Isopropyl, butyl, isobutyl, S-butyl, t-butyl, pentyl, hexyl, heptyl, octyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, etc. Examples of the group include a phenyl group and a naphthyl group. These groups may have a substituent, and examples of such a substituent include a phenyl group such as a phenyl group, a tolyl group and a xylyl group.

Specific examples of the compound represented by the general formula (IV) include, for example, alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide; calcium hydroxide, magnesium hydroxide, and barium hydroxide. Alkaline earth metal hydroxides such as lithium methoxide, sodium methoxide, sodium isopropoxide, sodium s-butoxide, sodium phenoxide, sodium benzyloxide, potassium methoxide, potassium ethoxide, potassium isopropoxide , Potassium s-butoxide, potassium t-butoxide, potassium phenoxide, potassium benzyloxide, magnesium methoxide, magnesium ethoxide, magnesium isopropoxide, magnesium s-butoxide, magnesium t-butoxide, mag Nesium phenoxide, magnesium benzyl oxide, calcium methoxide, calcium methoxide, calcium isopropoxide, calcium s butoxide, calcium t butoxide, calcium phenoxide, calcium benzyl oxide and the like.

[0025] Specific examples of the compound represented by the general formula (V) include, for example, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetra-n-propylammonium hydroxide, triisopropylammonium hydroxide, and tetra-n-ammonium hydroxide. —Butylammonium hydroxide, benzyltrimethylammonium hydroxide, tetramethylammonium methoxide, tetramethylammonium methoxide, tetramethylammonium n-propoxide, tetramethylammonium phenoxide, tetraethylammonium Methoxide, tetraethylammonium methoxide, tetraethylammonium propoxide, tetraethylammonium phenoxide, tetra_n-propylammonium methoxide, tetra-n- Propylammonium methoxide, triisopropylammonium methoxide, triisopropylammonium methoxide, tetra-n-butylammonium methoxide, tetra_n_butylammonium methoxide, tetra_n-butylammonium Mphenoxide, benzyltrimethylammonium methoxide, benzyltrimethylammonium methoxide, benzyl Rutrimethylammonium phenoxide and the like.

Specific examples of the compound represented by the general formula (VI) include, for example, tetramethylphosphonium hydroxide, tetraethylphosphonium hydroxide, tetra-n-propylphosphonium hydroxide, triisopropylphosphonium hydroxide, I-n-butylphosphonium hydroxide, benzinoletrimethinolephosphonium hydroxide, tetraphenylphosphonium methoxide, tetramethylphosphonium methoxide, tetraethylphosphonium methoxide, tetra_n-propylphosphonium methoxide, Triisopropylphosphonium methoxide, tetra-n_butylphosphonium methoxide, tetra-n_butylphosphonium methoxide, tetra-n_butylphosphonium phenoxide, benzyltrimethylphosphonium methoxide · The Sid, tetraphenyl phosphonyl © beam methoxide, tetraphenyl phosphonyl © Mue butoxide, etc. tetra- phenyl phosphonyl © Muhu enoki Sid and the like.

[0027] The amount of the basic substance used is preferably in the range of 0 :! to 10000 mol per 1 mol of palladium atom in the palladium compound: in the range of! To 3000 mol. Is more preferred.

[0028] The present invention can be carried out in the presence or absence of a solvent. Examples of strong solvents include hydrocarbons such as butane, isobutane, butene, isobutene, pentane, hexane, cyclohexane, benzene, toluene, and xylene; halogens such as dichloromethane, 1,2-dichloroethane, and chloroform. Hydrocarbons; ethers such as tetrahydrofuran, dipentyl ether, dihexyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethylene ether, and tetraethylene glycol dimethyl ether; formamide, acetoamide, N, N dimethylformamide, 1-methyl 2-pyrrolidinone Amides and the like. One type of solvent may be used alone, or two or more types may be used in combination. When the reaction is carried out in the presence of a solvent, the amount of the solvent used is not particularly limited, but is usually in the range of 0.01 to 10 times the mass of the conjugated diene compound.

[0029] The reaction temperature is preferably in the range of 0 to: 150 ° C, more preferably in the range of 20 to: 110 ° C. When the temperature is lower than 0 ° C, the reaction rate tends to be extremely slow, and when the temperature exceeds 150 ° C, by-products tend to increase.

The reaction pressure is preferably in the range from 0 :! to 3 MPa. The reaction is preferably performed in an atmosphere of an inert gas such as nitrogen or argon.

In the present invention, during the telomerization reaction, specifically, when the conversion of the conjugated diene compound exceeds 35%, more preferably 50%, and even more preferably 70%, the phosphine compound (II I) Is added. As a result, it is possible to suppress a decrease in the reaction rate due to a decrease in the concentration of the remaining conjugated conjugate, or to increase the reaction rate, thereby increasing the conversion of the conjugated gen compound in the reaction system. . In particular, the method of the present invention is excellent in that such effects can be obtained when a low-purity conjugated diene compound is used, for example, when “crude butadiene” is used. According to the present invention, the conversion and selectivity can be improved by adding the phosphine compound (III) during the telomerization reaction, as described above, without adding the phosphine compound (III) from the beginning. At the same time.

After the addition of the phosphine compound (III), the reaction may proceed more smoothly by increasing the reaction temperature by 1 to 10 ° C. before the addition.

The conversion of the conjugated diene compound can be measured by extracting a part of the reaction mixture and conducting gas chromatography analysis described later.

In the above general formula (III), R ³

The number of carbon atoms represented by R ^5. 1 to: The 10 alkyl group such as methyl group, Echiru radical, n-propyl group, an isopropyl radical, n-butyl group, Isobuchi Le group, t-butyl radical, n-heptyl group, n- Octyl, n-nonyl, n-decyl and the like.

[0032] Specific examples of the phosphine compound (III) include, for example, trimethylphosphine, triethylphosphine, tripropylphosphine, triisopropylphosphine, tributylphosphine, triisobutylphosphine, triisopentylphosphine, trihexylphosphine, tricyclohexylphosphine. , Trioctylphosphine, tridecylphosphine and the like. The amount of the phosphine compound (III) to be used is preferably 0.01 to 100 mol per mol of palladium atom in the palladium compound, and is preferably in the range of 0.05 to 10 mol. 0.:! More preferably in the range of 5 moles. If the amount is less than 0.01 mol, the reaction rate will not be improved. On the other hand, if it exceeds 100 mol, the effect corresponding thereto will be weak and the burden on the economy will increase, which is not preferable.

In the present invention, water may be added simultaneously with the addition of the phosphine compound (III). . By adding water, it is possible to suppress a decrease in selectivity due to coordination of the phosphine compound (III) and the isocyanide compound (II).

When water is added, the amount of addition is preferably in the range of 10 to 10,000 mol per 1 mol of palladium atoms in the palladium compound, and is preferably in the range of 20 to 5000 mol. From the point of view of speed, it is more preferred that the range be 50 to 2000 mol.

In the present invention, there is no particular limitation on the method of adding the phosphine compound (III) and water. May be added.

[0034] The reaction time depends on the type and amount of the hydroxyl hydride compound (I), the conjugated diene compound, the isocyanide compound (II), the palladium compound, the basic substance and the phosphine compound (III), the reaction temperature and the reaction pressure, and the like. Different forces Usually, the range of 0.5 to 10 hours before addition of the phosphine compound (III) and the range of 0.5 to 10 hours after addition of the phosphine compound (III).

There is no particular limitation on the method of carrying out the present invention, and for example, it can be carried out either in a batch system or a continuous system. In the case of the continuous type, the reaction can be performed even if the piston flow type reactor or the complete mixing tank type reactor is shifted, or a combination thereof can be performed.

As a specific reaction method, in a batch method, for example, under a nitrogen atmosphere, a hydroxynole compound (I), a basic substance, a palladium compound, an isocyanide ligated compound (II) and, if necessary, a solvent are mixed, A conjugated gen compound is added to the obtained mixture, and the mixture is reacted at a predetermined temperature and a predetermined pressure for a predetermined time. Then, the phosphine compound (III) and, if necessary, water are added to the reaction system. The reaction can be carried out.

In the continuous method, for example, under a nitrogen atmosphere, a hydroxyl conjugate (1), a basic substance, a palladium compound, an isocyanide compound (II) and, if necessary, a solvent are mixed. Is added. The resulting mixture is continuously or intermittently transferred to the first tank and reacted for a predetermined time. After the reaction in the first tank, the reaction liquid is continuously or intermittently withdrawn, and the phosphine compound (III) and, if necessary, The water can be transferred to the second tank continuously or intermittently after the addition of water, and further reacted for a predetermined time. [0036] After completion of the reaction, ethers can be separated and purified from the reaction mixture obtained by a conventional method for separating and purifying organic compounds. For example, after distilling off the unreacted raw materials and the solvent added as necessary, the catalyst component is separated from the residue by thin-film distillation, decantation, extraction, adsorption, etc. as necessary, and the resulting residue is obtained. By purifying the product by distillation, recrystallization or column chromatography, ethers with high purity can be obtained.

Example

Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited to these examples. The gas chromatographic analysis in each example and comparative example was performed according to the following procedure.

[Gas chromatography analysis]

Equipment: GC-14B (manufactured by Shimadzu Corporation)

Column used: DB—WAX (lOm) (Agilent Technologies)

Analysis conditions: injection temp. 220 ° C, detection temp. 250 ° C, temperature rise condition; hold at 40 ° C for 8 minutes → heat up at 15 ° C / min → hold at 240 ° C for 30 minutes

The component distribution of “crude butadiene” used in Examples and Comparative Examples is shown below.

[Components in crude butadiene]

1, 3 _ butadiene: 41.1 mass ^_0/0, 1, 2 _ Butadiene: 0.3 mass ^_0/0,

Butenes: 43.0% by mass, butanes: 10.3% by mass,

Acetylenes: 0.04 mass%, Other: 5.26 mass ^_0/0

Example 1

In a nitrogen atmosphere, 23.7 g (0.74 mol) of methanol, 12.8 mg (0.24 mmol) of sodium methoxide, 0.98 mg (0.012 mmol) of t-butynoleisocyanide, palladium in a 100 ml three-necked flask under a nitrogen atmosphere 0.72 mg (0.0024 mmol) of acetyl acetonate was dissolved to obtain a mixed solution. The obtained mixture was charged in a 100 mL autoclave equipped with a stirrer under a nitrogen atmosphere, and then 30 mL (18.9 g, 0.35 mol) of liquid 1,3-butadiene was charged by pressure. The mixture was heated with stirring, and after reaching 100 ° C., was stirred at the same temperature for 3 hours. Gas chromatography analysis shows that at this point 1,3-pig Gen conversion was confirmed to be 74%. Thereafter, 0.56 g (0.0047 mmol) of triethylphosphine, 7 ^ 42.6 mg (2.4 mmol) and 2.37 g (0.074 mol) of methanol were added, and the mixture was further stirred at 100 ° C for 3 hours.

A part of the obtained reaction mixture was extracted and analyzed by gas chromatography. The conversion of 1,3-butadiene was 98%, and the selectivity of 1-methoxy-1,2,7-octadiene was 1%. The selectivity for 3-methoxy-1,7-octadiene was 5.9%, and the selectivity for bürsik-mouth hexene and 1,3,7-otatatriene was less than 3% in total.

Example 2>

Sequence of execution: U was prepared in the same manner as in Example 1 except that 0.95 g (0.0047 mmol) of tributyl phosphine was used instead of 0.56 g (0.0047 mmol) of triethynolephosphine. Reaction and analysis were performed. The conversion of 1,3-butadiene is 98%, the selectivity for 1-methoxy-1,2,7-octadiene is 87.8%, and the selectivity for 3-methoxy-1,1,7-octadiene is 98%. The selectivity of vinylcyclohexene and 1,3,7-otatatriene was less than 3% in total.

Row f: U-core, 0.56 g (0.0047 mmol) of triethynolephosphine, 42.6 mg (2.4 mmol) of water and 3.0 mL (2.37 g) of methanol The reaction and analysis were carried out as in Example 1 except that only 0.56 g (0.0047 mmol and 3.0 mL (2.37 g) of methanol were added. The conversion of 1,3 butadiene was 98%. The selectivity of 1-methoxy-2,7-octadiene was 87.5%, the selectivity of 3-methoxy1,7-octadiene was 10.5%, and the selectivity of vinylcyclohexene and 1,3,7-otatatriene The rate was less than 2% in total.

Example 4>

Execution sequence: The reaction and analysis were performed in the same manner as in Example 1 except that 42.6 mg (2.4 mmol) of water and 85.2 mg (4.8 mmol) of water were added. The conversion of 1,3-butadiene was 99%, and the selectivities of 1-methoxy-1,2,7-octadiene and 3-methoxy-1,7,7-octadiene were 90.3% and 5.1%. The selectivity for bulcyclohexene and 1,3,7-otatatriene was less than 3% in total. <Example 5>

Under a nitrogen atmosphere, 33.7 g (0.74 mol) of methanol, 12.8 mg (0.24 mmol) of sodium methoxide, 0.98 mg (0.012 mmol) of t-butyl isocyanide, palladium acetyl 0.72 mg (0.20024 mmol) of acetonato was dissolved to obtain a mixed solution. The obtained mixture is charged in an autoclave having an internal volume of 100 mL equipped with a stirrer under a nitrogen atmosphere, and then 77 mL of liquid "crude butadiene" (18.9 g of 1,3-butadiene, equivalent to 0.35 mol) is added. It was pumped and charged. The mixture was heated with stirring, and after reaching 100 ° C, the mixture was stirred at the same temperature for 3 hours. Gas chromatography analysis confirmed that the conversion of 1,3-butadiene was 52% at this time. Thereafter, 0.56 g (0.0047 mmol) of triethynolephosphine, 42.6 mg (2.4 mmol) of water and 2.37 g (0.074 mol) of methanol were added to the mixture, and the mixture was kept at 100 ° C for 3 more minutes. Stirred for hours.

A part of the obtained reaction mixture was sampled and analyzed by gas chromatography. The conversion of 1,3-butadiene in the crude butadiene was 98%, and the selectivity for 1-methoxy 2,7-otatagene was 89%. The selectivity for 1%, 3-methoxy 1,7 octadiene is 6.1%, and the selectivity for vinylcyclohexene and 1,3,7-otatatriene is less than 3% in total.

Under a nitrogen atmosphere, 23.7 g (0.74 mol) of methanol, 12.8 mg (0.24 mmol) of sodium methoxide, 0.98 mg (0.02 mmol) of t-butyl isocyanide, palladium acetyl acetate 0.72 mg (0.0024 mmol) of nate and 0.56 g (0.0047 mmol) of triethylphosphine were mixed, and 30 mL (18.9 g, 0.35 mol) of 1,3-butadiene was charged under pressure. The mixture was heated with stirring, and after reaching 100 ° C, the mixture was stirred at the same temperature for 3 hours. A part of the reaction mixture was sampled and analyzed by gas chromatography. The conversion of 1,3-butadiene was 98%, and the selectivity of 1-methoxy-1,2,7-octadiene was 59.4%, 3 The selectivity for methoxy-1,7-octadiene was 34.7%, and the selectivity for bulcyclohexene and 1,3,7-otatatriene was less than 3% in total.

Under a nitrogen atmosphere, 23.7 g (0.74 mol) of methanol was placed in a 100 ml three-necked flask. 12.8 mg (0.24 mmol) of thorium methoxide, 0.98 mg (0.012 mmol) of t-butyl isocyanide, 0.72 mg (0.20024 mmol) of palladium acetyl acetonate were dissolved to obtain a mixed solution. . The obtained mixture is charged in an autoclave having an internal volume of 100 mL equipped with a stirrer under a nitrogen atmosphere, and then 77 mL of liquid "crude butadiene" (18.9 g of 1,3-butadiene, equivalent to 0.35 mol) is added. It was pumped and charged. The mixture was heated with stirring, and after reaching 100 ° C., the mixture was stirred at the same temperature for 6 hours.

A part of the obtained reaction mixture was extracted and subjected to gas chromatography analysis. The conversion of 1,3-butadiene in the crude butadiene was 48%, and the selection of 1-methoxy-1,2,7-otatagene was performed. The selectivity was 90.1%, the selectivity for 3-methoxy-1,7-octadiene was 3.1%, and the selectivity for bulcyclohexene and 1,3,7-otatatriene was less than 3% in total.

From Examples 1 to 4 and Comparative Example 1, when the isocyanide compound (II) and the phosphine compound (III) were added together from the beginning, the selectivity of the target compound was low, and when the method of the present invention was followed. Was found to greatly increase the selectivity of the target compound. Also, from Example 5 and Comparative Example 2, when “crude butadiene” was used as a raw material, the phosphine conjugate (III) was added to the reaction system during the telomerization reaction (Example 5). It can be seen that the conversion was greatly improved and the reaction rate was improved as compared with the case where no addition was made (Comparative Example 2).

Claims

Claims [1] General formula (I)

[Formula 1] R'OH (I)

In the telomerization reaction of the conjugated conjugate in the presence of the hydroxy compound represented by the formula, first, a palladium compound, a general formula (II)

[Formula 2] R ² NC (II)

The above reaction is carried out in the presence of a tertiary isocyanide compound represented by

And then general formula (III)

[Chemical Formula 3] PR ³ R ⁴ R ⁵ (III)

(Wherein, R ³ , R ⁴ and R ⁵ each independently represent an alkyl group having from! To 10 carbon atoms.) A tertiary phosphine compound represented by the formula: A method for producing ethers.

[2] The method for producing ethers according to claim 1, wherein the tertiary phosphine compound is added after the conversion of the conjugated diene compound reaches 35% or more.

[3] The method for producing ethers according to claim 1 or claim 2, wherein the conjugated diene compound is 1,3-butadiene or isoprene.

[4] The method for producing ethers according to claim 1 or 2, wherein the conjugated diene compound is crude butadiene.

[5] The method for producing ethers according to any one of [1] to [4], wherein water is added simultaneously with the addition of the tertiary phosphine compound.